Thick-film pastes containing lead-tellurium-lithium-oxides, and their use in the manufacture of semiconductor devices

ABSTRACT

The present invention provides a thick-film paste for printing the front side of a solar cell device having one or more insulating layers. The thick-film paste comprises an electrically conductive metal, and a lead-tellurium-lithium-oxide dispersed in an organic medium.

FIELD OF THE INVENTION

The present invention provides a thick-film paste for printing the frontside of a solar cell device having one or more insulating layers. Thethick-film paste comprises a source of an electrically conductive metalor derivative thereof, and a lead-tellurium-lithium-oxide dispersed inan organic medium.

TECHNICAL BACKGROUND

A conventional solar cell structure with a p-type base has a negativeelectrode that is typically on the front side (sun side) of the cell anda positive electrode on the back side. Radiation of an appropriatewavelength falling on a p-n junction of a semiconductor body serves as asource of external energy to generate electron-hole pair chargecarriers. These electron-hole pair charge carriers migrate in theelectric field generated by the p-n semiconductor junction and arecollected by a conductive grid or metal contact applied to the surfaceof the semiconductor. The current generated flows to the externalcircuit.

Conductive pastes (also known as inks) are typically used to form theconductive grids or metal contacts. Conductive pastes typically includea glass frit, a conductive species (e.g., silver particles), and anorganic medium. To form the metal contacts, conductive pastes areprinted onto a substrate as grid lines or other patterns and then fired,during which electrical contact is made between the grid lines and thesemiconductor substrate.

However, crystalline silicon PV cells are typically coated with ananti-reflective coating such as silicon nitride, titanium oxide, orsilicon oxide to promote light adsorption, which increases the cells'efficiency. Such anti-reflective coatings also act as an insulator,which impairs the flow of electrons from the substrate to the metalcontacts. To overcome this problem, the conductive paste shouldpenetrate the anti-reflective coating during firing to form metalcontacts having electrical contact with the semiconductor substrate.Formation of a strong bond between the metal contact and the substrate(i.e., adhesion) and solderability are also desirable.

The ability to penetrate the anti-reflective coating and form a strongbond with the substrate upon firing is highly dependent on thecomposition of the conductive paste and firing conditions. Efficiency, akey measure of PV cell performance, is also influenced by the quality ofthe electrical contact made between the fired conductive paste and thesubstrate.

To provide an economical process for manufacturing PV cells with goodefficiency, there is a need for thick-film paste compositions that canbe fired at low temperatures to penetrate an anti-reflective coating andprovide good electrical contact with the semiconductor substrate.

SUMMARY

One aspect of the present invention is a thick-film paste compositioncomprising:

-   -   a) 85 to 99.75% by weight of an electrically conductive metal or        derivative thereof, based on total solids in the composition;    -   b) 0.25 to 15% by weight based on solids of a        lead-tellurium-lithium-oxide; and    -   c) an organic medium.

Another aspect of the present invention is a process comprising:

-   (a) providing a semiconductor substrate comprising one or more    insulating films deposited onto at least one surface of the    semiconductor substrate;-   (b) applying a thick-film paste composition onto the one or more    insulating films to form a layered structure, wherein the thick-film    paste composition comprises:    -   i) 85 to 99.75% by weight based on solids of a source of an        electrically conductive metal;    -   ii) 0.25 to 15% by weight based on solids of a        lead-tellurium-lithium-oxide; and    -   iii) an organic medium; and-   (c) firing the semiconductor substrate, one or more insulating    films, and thick-film paste, forming an electrode in contact with    the one or more insulating layers and in electrical contact with the    semiconductor substrate.

Another aspect of this invention is an article comprising:

-   -   a) a semiconductor substrate;    -   b) one or more insulating layers on the semiconductor substrate;        and    -   c) an electrode in contact with the one or more insulating        layers and in electrical contact with the semiconductor        substrate, the electrode comprising an electrically conductive        metal and lead-tellurium-lithium-oxide.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A through 1F provide a process flow diagram illustrating stepsemployed the fabrication of a semiconductor device in an embodiment ofthe present disclosure.

FIG. 1A depicts a substrate used in the fabrication of a photovoltaicdevice;

FIG. 1B depicts application of an n-type diffusion layer;

FIG. 1C depicts removal of the n-type diffusion layer from most surfacesof the substrate;

FIG. 1D depicts application of an insulating, anti-reflection coating;

FIG. 1E depicts printing of a thick-film paste composition; and

FIG. 1F depicts formation of electrodes of the photovoltaic device.

Reference numerals shown in the various views of FIGS. 1A through 1F areexplained below.

-   10: p-type silicon substrate-   20: n-type diffusion layer-   30: insulating film-   40: p+ layer (back surface field, BSF)-   60: aluminum paste deposited on back side-   61: aluminum back electrode (obtained by firing back-side aluminum    paste)-   70: silver or silver/aluminum paste deposited on back side-   71: silver or silver/aluminum back electrode (obtained by firing    back-side silver paste)-   500: thick-film paste deposited on front side-   501: front electrode (formed by firing the thick-film paste)

DETAILED DESCRIPTION

Solar-powered photovoltaic systems are considered to be environmentallyfriendly in that they reduce the need for fossil fuels.

The present invention provides compositions that can be used tomanufacture photovoltaic devices with improved electrical performance.The thick-film paste composition comprises:

-   -   a) 85 to 99.75% by weight of an electrically conductive metal or        derivative thereof, based on total solids in the composition;    -   b) 0.25 to 15% by weight based on solids of a        lead-tellurium-lithium-oxide; and    -   c) an organic medium.

As defined herein, the organic medium is not considered to be part ofthe solids comprising the thick-film paste composition.

Electrically Conductive Metal

The electrically conductive metal is selected from the group consistingof silver, copper, and palladium. The electrically conductive metal canbe in a flake form, a spherical form, a granular form, a crystallineform, a powder, or other irregular forms and mixtures thereof. Theelectrically conductive metal can be provided in a colloidal suspension.

When the metal is silver, it can be in the form of silver metal, silverderivatives, or mixtures thereof. Exemplary derivatives include: alloysof silver, silver oxide (Ag₂O), silver salts such as AgCl, AgNO₃,AgOOCCH₃ (silver acetate), AgOOCF₃ (silver trifluoroacetate), silverorthophosphate (Ag₃PO₄), for example. Other forms of silver compatiblewith the other thick-film paste components can also be used.

In one embodiment, the electrically conductive metal or derivativesthereof is from about 85 to about 99.75 wt % of the solid components ofthe thick-film paste composition. In a further embodiment, the source ofthe electrically conductive metal or derivatives thereof is from about90 to about 95 wt % of the solid components of the thick-film pastecomposition.

In an embodiment, the solids portion of the thick-film paste compositionincludes about 85 to about 99.5 wt % spherical silver particles. In oneembodiment, the solids portion of the thick-film paste compositionincludes about 85 to about 90 wt % silver particles and about 1 to about9.5 wt % silver flakes.

In one embodiment, the thick-film paste composition comprises coatedsilver particles that are electrically conductive. Suitable coatingsinclude phosphate and surfactants. Suitable surfactants includepolyethyleneoxide, polyethyleneglycol, benzotriazole,poly(ethyleneglycol)acetic acid, lauric acid, oleic acid, capric acid,myristic acid, linolic acid, stearic acid, palmitic acid, stearatesalts, palmitate salts, and mixtures thereof. The salt counter-ions canbe ammonium, sodium, potassium, and mixtures thereof.

The particle size of the silver is not subject to any particularlimitation. In one embodiment, an average particle size is 0.5-10microns; in another embodiment, the average particle size is 1-5microns.

As used herein, “particle size” or “D₅₀” is intended to mean “averageparticle size”; “average particle size” means the 50% volumedistribution size. Volume distribution size may be determined by anumber of methods understood by one of skill in the art, including butnot limited to laser diffraction and dispersion method using a Microtracparticle size analyzer (Largo, Fla.).

Lead-Tellurium-Lithium-Oxide Compositions

An aspect of the invention relates to lead-tellurium-lithium-oxide(Pb—Te—Li—O) compositions. In an embodiment, these compositions may beglass compositions. In a further embodiment, these compositions may becrystalline, partially crystalline, amorphous, partially amorphous, orcombinations thereof. In an embodiment, the Pb—Te—Li—O composition mayinclude more than one glass composition. In an embodiment, thePb—Te—Li—O composition may include a glass composition and an additionalcomposition, such as a crystalline composition. The terms “glass” or“glass composition” will be used herein to represent any of the abovecombinations of amorphous and crystalline materials.

In an embodiment, glass compositions described herein includelead-tellurium-lithium-oxide. The glass compositions may also includeadditional components such as silicon, silver, tin, bismuth, aluminum,cerium, zirconium, sodium, vanadium, flourine, niobium, sodium,tantalum, potassium, magnesium, phosphorus, selenium, cobalt, palladium,ruthenium, nickel, manganese, chromium, and the like.

The lead-tellurium-lithium-oxide (Pb—Te—Li—O) may be prepared by mixingPbO, TeO₂, and Li₂O (or other materials that decompose into the desiredoxides when heated) using techniques understood by one of ordinary skillin the art. Such preparation techniques may involve heating the mixturein air or an oxygen-containing atmosphere to form a melt, quenching themelt, and grinding, milling, and/or screening the quenched material toprovide a powder with the desired particle size. Melting the mixture oflead, tellurium, and lithium oxides is typically conducted to a peaktemperature of 800 to 1200° C. The molten mixture can be quenched, forexample, on a stainless steel platen or between counter-rotatingstainless steel rollers to form a platelet. The resulting platelet canbe milled to form a powder. Typically, the milled powder has a D₅₀ of0.1 to 3.0 microns. One skilled in the art of producing glass frit mayemploy alternative synthesis techniques such as but not limited to waterquenching, sol-gel, spray pyrolysis, or others appropriate for makingpowder forms of glass.

In an embodiment, the starting mixture used to make the Pb—Te—Li—O mayinclude (based on the weight of the total starting mixture): PbO thatmay be 30 to 60 wt %, 40 to 55 wt %, or 45 to 50 wt %; TeO₂ that may be40 to 65 wt %, 45 to 60 wt %, or 50 to 55 wt %; and Li₂O that may be 0.1to 5 wt %, 0.2 to 3 wt %, or 0.3 to 1 wt %.

In a further embodiment, in addition to the above PbO, TeO₂, and Li₂O,the starting mixture used to make the Pb—Te—Li—O may include one or moreof SiO₂, SnO₂, B₂O₃, Ag₂O, BiF₃, V₂O₅, Na₂O, ZrO₂, CeO₂, Bi₂O₃, Nb₂O₅,Ta₂O₅, K₂O, MgO, P₂O₅, SeO₂, Co₃O₄, PdO, RuO₂, NiO, MnO, Cr₂O₃, orAl₂O₃. In aspects of this embodiment (based on the weight of the totalstarting mixture):

the SiO₂ may be 0 to 11 wt %, 0 to 5 wt %, 0.25 to 4 wt %, or 0 to 0.5wt %;

the SnO₂ may be 0 to 5 wt %, 0 to 2 wt %, or 0.5 to 1.5 wt %;

the B₂O₃ may be 0 to 10 wt %, 0 to 5 wt %, or 0.5 to 5 wt %;

the Ag₂O may be 0 to 30 wt %, 0 to 20 wt %, 3 to 15 wt % or 1 to 8 wt %;

the TiO₂ may be 0 to 5 wt %, 0.25 to 5 wt %, or 0.25 to 2.5 wt %;

the PbF₂ may be 0 to 20 wt %, 0 to 15 wt %, or 5 to 10 wt %;

the BiF₃ may be 0 to 15 wt %, 0 to 10 wt %, or 1 to 10 wt %;

the ZnO may be 0 to 5 wt %, 0 to 3 wt %, or 2 to 3 wt %;

the V₂O₅ may be 0 to 5 wt %, 0 to 1 wt %, or 0.5 to 1 wt %;

the Na₂O may be 0 to 5 wt %, 0 to 3 wt %, or 0.1 to 1.5 wt %;

the CuO may be 0 to 5 wt %, 0 to 3 wt %, or 2 to 3 wt %;

the ZrO₂ may be 0 to 3 wt %, 0 to 2 wt %, or 0.1 to 1 wt %;

the CeO₂ may be 0 to 5 wt %, 0 to 3 wt %, or 0.1 to 2.5 wt %;

the Bi₂O₃ may be 0 to 15 wt %, 0 to 10 wt %, or 5 to 8 wt %; and

the Al₂O₃ may be 0 to 3 wt %, 0 to 2 wt %, or 0.1 to 2 wt %.

In an embodiment, the Pb—Te—Li—O may be a homogenous powder. In afurther embodiment, the Pb—Te—Li—O may be a combination of more than onepowder, wherein each powder may separately be a homogenous population.The composition of the overall combination of the two powders may bewithin the ranges described above. For example, the Pb—Te—Li—O mayinclude a combination of two or more different powders; separately,these powders may have different compositions, and may or may not bewithin the ranges described above; however, the combination of thesepowders may be within the ranges described above.

In an embodiment, the Pb—Te—Li—O composition may include one powderwhich includes a homogenous powder including some but not all of theelements of the group Pb, Te, Li, and O, and a second powder, whichincludes one or more of the elements of the group Pb, Te, Li, and O.

In an embodiment, some or all of the Li₂O may be replaced with Na₂O,K₂O, Cs₂O, or Rb₂O, resulting in a glass composition with propertiessimilar to the compositions listed above. In this embodiment, the totalalkali metal oxide content may be 0 to 5 wt %, 0.1 to 3 wt %, or 0.25 to3 wt %.

In a further embodiment, the glass frit composition(s) herein mayinclude one or more of a third set of components: GeO₂, Ga₂O₃, In₂O₃,NiO, CoO, ZnO, CaO, MgO, SrO, MnO, BaO, SeO₂, MoO₃, WO₃, Y₂O₃, As₂O₃,La₂O₃, Nd₂O₃, Bi₂O₃, Ta₂O₅, V₂O₅, FeO, HfO₂, Cr₂O₃, CdO, Sb₂O₃, PbF₂,ZrO₂, Mn₂O₃, P₂O₅, CuO, La₂O₃, Pr₂O₃, Nd₂O₃, Gd₂O₃, Sm₂O₃, Dy₂O₃, Eu₂O₃,Ho₂O₃, Yb₂O₃, Lu₂O₃, CeO₂, BiF₃, SnO, SiO₂, Ag₂O, Nb₂O₅, TiO₂, and metalhalides (e.g., NaCl, KBr, NaI, LiF).

Therefore as used herein, the term “Pb—Te—Li—O” may also include metaloxides that contain one or more elements selected from the groupconsisting of Si, Sn, Ti, Ag, Na, K, Rb, Cs, Ge, Ga, In, Ni, Zn, Ca, Mg,Sr, Ba, Se, Mo, W, Y, As, La, Nd, Co, Pr, Gd, Sm, Dy, Eu, Ho, Yb, Lu,Bi, Ta, V, Fe, Hf, Cr, Cd, Sb, Bi, F, Zr, Mn, P, Cu, Ce, and Nb.

Table 1, 2, and 4 lists some examples of powder mixtures containing PbO,TeO₂, Li₂O, and other optional compounds that can be used to makelead-tellurium-lithium-oxides. This list is meant to be illustrative,not limiting. In Table 1, 2, and 4, the amounts of the compounds areshown as weight percent, based on the weight of the total glasscomposition.

Typically, the mixture of PbO and TeO₂ powders comprises 5 to 95 mol %of lead oxide and 5 to 95 mol % of tellurium oxide, based on thecombined powders. In one embodiment, the mixture of PbO and TeO₂ powderscomprises 25 to 50 mol % of lead oxide and 50 to 75 mol % of telluriumoxide, based on the combined powders.

Glass compositions, also termed glass frits, are described herein asincluding percentages of certain components. Specifically, thepercentages are the percentages of the components used in the startingmaterial that was subsequently processed as described herein to form aglass composition. Such nomenclature is conventional to one of skill inthe art. In other words, the composition contains certain components,and the percentages of those components are expressed as a percentage ofthe corresponding oxide form. As recognized by one of ordinary skill inthe art in glass chemistry, a certain portion of volatile species may bereleased during the process of making the glass. An example of avolatile species is oxygen.

If starting with a fired glass, one of ordinary skill in the art maycalculate the percentages of starting components described herein usingmethods known to one of skill in the art including, but not limited to:Inductively Coupled Plasma-Emission Spectroscopy (ICPES), InductivelyCoupled Plasma-Atomic Emission Spectroscopy (ICP-AES), and the like. Inaddition, the following exemplary techniques may be used: X-RayFluorescence spectroscopy (XRF); Nuclear Magnetic Resonance spectroscopy(NMR); Electron Paramagnetic Resonance spectroscopy (EPR); Mössbauerspectroscopy; electron microprobe Energy Dispersive Spectroscopy (EDS);electron microprobe Wavelength Dispersive Spectroscopy (WDS);Cathodo-Luminescence (CL).

One of ordinary skill in the art would recognize that the choice of rawmaterials could unintentionally include impurities that may beincorporated into the glass during processing. For example, theimpurities may be present in the range of hundreds to thousands ppm.

The presence of the impurities would not alter the properties of theglass, the thick film composition, or the fired device. For example, asolar cell containing the thick-film composition may have the efficiencydescribed herein, even if the thick-film composition includesimpurities.

Organic Medium

The inorganic components of the thick-film paste composition are mixedwith an organic medium to form viscous pastes having suitableconsistency and rheology for printing. A wide variety of inert viscousmaterials can be used as the organic medium. The organic medium can beone in which the inorganic components are dispersible with an adequatedegree of stability during manufacturing, shipping and storage of thepastes, as well as on the printing screen during the screen-printingprocess.

Suitable organic media have rheological properties that provide stabledispersion of solids, appropriate viscosity and thixotropy for screenprinting, appropriate wettability of the substrate and the paste solids,a good drying rate, and good firing properties. The organic medium cancontain thickeners, stabilizers, surfactants, and/or other commonadditives. The organic medium can be a solution of polymer(s) insolvent(s). Suitable polymers include ethyl cellulose, ethylhydroxyethylcellulose, wood rosin, mixtures of ethyl cellulose and phenolic resins,polymethacrylates of lower alcohols, and the monobutyl ether of ethyleneglycol monoacetate. Suitable solvents include terpenes such as alpha- orbeta-terpineol or mixtures thereof with other solvents such as kerosene,dibutylphthalate, butyl carbitol, butyl carbitol acetate, hexyleneglycol and alcohols with boiling points above 150° C., and alcoholesters. Other suitable organic medium components include:bis(2-(2-butoxyethoxy)ethyl adipate, dibasic esters such as DBE, DBE-2,DBE-3, DBE-4, DBE-5, DBE-6, DBE-9, and DBE 1B, octyl epoxy tallate,isotetradecanol, and pentaerythritol ester of hydrogenated rosin. Theorganic medium can also comprise volatile liquids to promote rapidhardening after application of the thick-film paste composition on asubstrate.

The optimal amount of organic medium in the thick-film paste compositionis dependent on the method of applying the paste and the specificorganic medium used. Typically, the thick-film paste compositioncontains 70 to 95 wt % of inorganic components and 5 to 30 wt % oforganic medium.

If the organic medium comprises a polymer, the polymer typicallycomprises 8 to 15 wt % of the organic composition.

Preparation of the Thick-Film Paste Composition

In one embodiment, the thick-film paste composition can be prepared bymixing the conductive metal powder, the Pb—Te—Li—O powder, and theorganic medium in any order. In some embodiments, the inorganicmaterials are mixed first, and they are then added to the organicmedium. The viscosity can be adjusted, if needed, by the addition ofsolvents. Mixing methods that provide high shear may be useful.

Another aspect of the present invention is a process comprising:

-   (a) providing an article comprising one or more insulating films    deposited onto at least one surface of a semiconductor substrate;-   (b) applying a thick-film paste composition onto at least a portion    of the one or more insulating films to form a layered structure,    wherein the thick-film paste composition comprises:    -   i) 85 to 99.75% by weight based on solids of a source of an        electrically conductive metal;    -   ii) 0.25 to 15% by weight based on solids of a        lead-tellurium-lithium-oxide; and    -   iii) an organic medium; and-   (c) firing the semiconductor substrate, one or more insulating    films, and thick-film paste wherein the organic medium of the thick    film paste is volatilized, forming an electrode in contact with the    one or more insulating layers and in electrical contact with the    semiconductor substrate.

In an embodiment, the thick film paste may includelead-tellurium-lithium-oxide in an amount of 0.25 to 15%, 0.5 to 7%, or1 to 3% by weight based on solids.

In one embodiment, a semiconductor device is manufactured from anarticle comprising a junction-bearing semiconductor substrate and asilicon nitride insulating film formed on a main surface thereof. Theprocess includes the steps of applying (for example, coating orscreen-printing) onto the insulating film, in a predetermined shape andthickness and at a predetermined position, a thick-film pastecomposition having the ability to penetrate the insulating layer, thenfiring so that thick-film paste composition reacts with the insulatingfilm and penetrates the insulating film, thereby effecting electricalcontact with the silicon substrate.

One embodiment of this process is illustrated in FIGS. 1A through 1F.

FIG. 1A shows a single-crystal silicon or multi-crystalline siliconp-type substrate 10.

In FIG. 1B, an n-type diffusion layer 20 of the reverse polarity isformed to create a p-n junction. The n-type diffusion layer 20 can beformed by thermal diffusion of phosphorus (P) using phosphorusoxychloride (POCl₃) as the phosphorus source. In the absence of anyparticular modifications, the n-type diffusion layer 20 is formed overthe entire surface of the silicon p-type substrate. The depth of thediffusion layer can be varied by controlling the diffusion temperatureand time, and is generally formed in a thickness range of about 0.3 to0.5 microns. The n-type diffusion layer may have a sheet resistivity ofseveral tens of ohms per square up to about 120 ohms per square.

After protecting one surface of the n-type diffusion layer 20 with aresist or the like, as shown in FIG. 1C, the n-type diffusion layer 20is removed from most surfaces by etching so that it remains only on onemain surface. The resist is then removed using an organic solvent or thelike.

Next, in FIG. 1D, an insulating layer 30 which also functions as ananti-reflection coating is formed on the n-type diffusion layer 20. Theinsulating layer is commonly silicon nitride, but can also be aSiN_(x):H film (i.e., the insulating film comprises hydrogen forpassivation during subsequent firing processing), a titanium oxide film,a silicon oxide film, a silicon nitride film containing carbon, asilicon oxide film containing carbon, a silicon oxynitride filmcontaining carbon, or a silicon oxide/titanium oxide film. A thicknessof about 700 to 900 Å of a silicon nitride film is suitable for arefractive index of about 1.9 to 2.0. Deposition of the insulating layer30 can be by sputtering, chemical vapor deposition, or other methods.

Next, electrodes are formed. As shown in FIG. 1E, a thick-film pastecomposition of this invention is screen-printed on the insulating film30, and then dried. In addition, aluminum paste 60 and back-side silverpaste 70 are screen-printed onto the back side of the substrate, andsuccessively dried. Firing is carried out at a temperature of 750 to850° C. for a period of from several seconds to several tens of minutes.

Consequently, as shown in FIG. 1F, during firing, aluminum diffuses fromthe aluminum paste into the silicon substrate on the back side, therebyforming a p+ layer 40, containing a high concentration of aluminumdopant. This layer is generally called the back surface field (BSF)layer, and helps to improve the energy conversion efficiency of thesolar cell. Firing converts the dried aluminum paste 60 to an aluminumback electrode 61. The back-side silver paste 70 is fired at the sametime, becoming a silver or silver/aluminum back electrode 71. Duringfiring, the boundary between the back-side aluminum and the back-sidesilver assumes the state of an alloy, thereby achieving electricalconnection. Most areas of the back electrode are occupied by thealuminum electrode, owing in part to the need to form a p+ layer 40. Atthe same time, because soldering to an aluminum electrode is impossible,the silver or silver/aluminum back electrode is formed on limited areasof the back side as an electrode for interconnecting solar cells bymeans of copper ribbon or the like.

On the front side, the thick-film paste composition 500 of the presentinvention sinters and penetrates through the insulating film 30 duringfiring, and thereby achieves electrical contact with the n-typediffusion layer 20. This type of process is generally called “firethrough.” This fired-through state, i.e., the extent to which the pastemelts and passes through the insulating film 30, depends on the qualityand thickness of the insulating film 30, the composition of the paste,and on the firing conditions. When fired, the paste 500 becomes theelectrode 501, as shown in FIG. 1F.

In one embodiment, the insulating film is selected from titanium oxide,aluminum oxide, silicon nitride, SiN_(x):H, silicon oxide, siliconcarbon oxynitride, a silicon nitride film containing carbon, a siliconoxide film containing carbon, and silicon oxide/titanium oxide films.The silicon nitride film can be formed by sputtering, plasma-enhancedchemical vapor deposition (PECVD), or a thermal CVD process. In oneembodiment, the silicon oxide film is formed by thermal oxidation,sputtering, or thermal CVD or plasma CVD. The titanium oxide film can beformed by coating a titanium-containing organic liquid material onto thesemiconductor substrate and firing, or by thermal CVD.

In one embodiment of this process, the semiconductor substrate can besingle-crystal or multi-crystalline silicon.

Suitable insulating films include one or more components selected from:aluminum oxide, titanium oxide, silicon nitride, SiN_(x):H, siliconoxide, silicon carbon oxynitride, a silicon nitride film containingcarbon, a silicon oxide film containing carbon, and siliconoxide/titanium oxide. In one embodiment of the invention, the insulatingfilm is an anti-reflection coating (ARC). The insulating film can beapplied to a semiconductor substrate, or it can be naturally forming,such as in the case of silicon oxide.

In one embodiment, the insulating film comprises a layer of siliconnitride. The silicon nitride can be deposited by CVD (chemical vapordeposition), PECVD (plasma-enhanced chemical vapor deposition),sputtering, or other methods.

In one embodiment, the silicon nitride of the insulating layer istreated to remove at least a portion of the silicon nitride. Thetreatment can be a chemical treatment. The removal of at least a portionof the silicon nitride may result in an improved electrical contactbetween the conductor of the thick-film paste composition and thesemiconductor substrate. This may result in improved efficiency of thesemiconductor device.

In one embodiment, the silicon nitride of the insulating film is part ofan anti-reflective coating.

The thick-film paste composition can be printed on the insulating filmin a pattern, e.g., bus bars with connecting lines. The printing can beby screen-printing, plating, extrusion, inkjet, shaped or multipleprinting, or ribbons.

In this electrode-forming process, the thick-film paste composition isheated to remove the organic medium and sinter the metal powder. Theheating can be carried out in air or an oxygen-containing atmosphere.This step is commonly referred to as “firing.” The firing temperatureprofile is typically set so as to enable the burnout of organic bindermaterials from the dried thick-film paste composition, as well as anyother organic materials present. In one embodiment, the firingtemperature is 750 to 950° C. The firing can be conducted in a beltfurnace using high transport rates, for example, 100-600 cm/min, withresulting hold-up times of 0.05 to 5 minutes. Multiple temperaturezones, for example 3 to 11 zones, can be used to control the desiredthermal profile.

Upon firing, the electrically conductive metal and Pb—Te—Li—O mixturepenetrate the insulating film. The penetration of the insulating filmresults in an electrical contact between the electrode and thesemiconductor substrate. After firing, an interlayer may be formedbetween the semiconductor substrate and the electrode, wherein theinterlayer comprises one or more of tellurium, tellurium compounds,lead, lead compounds, and silicon compounds, where the silicon mayoriginate from the silicon substrate and/or the insulating layer(s).After firing, the electrode comprises sintered metal that contacts theunderlying semiconductor substrate and may also contact one or moreinsulating layers.

Another aspect of the present invention is an article formed by aprocess comprising:

-   (a) providing an article comprising one or more insulating films    deposited onto at least one surface of a semiconductor substrate;-   (b) applying a thick-film paste composition onto at least a portion    of the one or more insulating films to form a layered structure,    wherein the thick-film paste composition comprises:    -   i) 85 to 99.75% by weight based on solids of a source of an        electrically conductive metal;    -   ii) 0.25 to 15% by weight based on solids of a        lead-tellurium-lithium-oxide; and    -   iii) an organic medium, and-   (c) firing the semiconductor substrate, one or more insulating    films, and thick-film paste wherein the organic medium of the thick    film paste is volatilized, forming an electrode in contact with the    one or more insulating layers and in electrical contact with the    semiconductor substrate.

Such articles may be useful in the manufacture of photovoltaic devices.In one embodiment, the article is a semiconductor device comprising anelectrode formed from the thick-film paste composition. In oneembodiment, the electrode is a front-side electrode on a silicon solarcell. In one embodiment, the article further comprises a back electrode.

EXAMPLES

Illustrative preparations and evaluations of thick-film pastecompositions are described below.

Example I Lead-Tellurium-Lithium-Oxide Preparation

Lead-Tellurium-Lithium-Oxide Preparation of Glasses 1-7 of Table 1, andGlasses in Tables 2 and 3

The lead-tellurium-lithium-oxide (Pb—Te—Li—O) compositions of Table 1were prepared by mixing and blending Pb₃O₄, TeO₂, and Li₂CO₃ powders.The blended powder batch materials were loaded in a platinum alloycrucible and then inserted into a furnace at 900-1000° C. using an airor O₂-containing atmosphere. The duration of the heat treatment was 20minutes following the attainment of a full solution of the constituents.The resulting low viscosity liquid resulting from the fusion of theconstituents was then quenched by metal roller. The quenched glass wasthen milled, and screened to provide a powder with a D₅₀ of 0.1 to 3.0microns.

The lead-tellurium-oxide (Pb—Te—Li—O) compositions of Table 2 wereprepared by mixing and blending Pb₃O₄, TeO₂, and Li₂CO₃ powders andoptionally, as shown in Table 2, SiO₂, Al₂O₃, ZrO₂, B₂O₃, Nb₂O₅, Na₂CO₃,Ta₂O₅, K₂CO₃, Ag₂O, AgNO₃, CeO₂, and/or SnO₂.

Lead-Tellurium-Lithium-Oxide Preparation of Glasses 8-14 of Table 1, andGlasses in Table 4

Mixtures of TeO₂ powder (99+% purity), PbO powder, and Li₂CO₃ powder(ACS reagent grade, 99+% purity) were tumbled in a suitable containerfor 15 to 30 minutes to mix the starting powders for the glasscompositions 8-14 of Table 1. For the compositions of Table 4, mixturesof TeO₂, PbO or Pb₃O₄, and Li₂CO₃ and optionally, as shown in Table 4,SiO₂, Bi₂O₃, BiF₃, SnO₂, Al₂O₃, MgO, Na₂O, Na₂CO₃, NaNO₃, P₂O₅, aluminumphosphate, lead phosphate, SeO₂, PbSeO₃, Co₃O₄, CoO, PdO, PdCO₃,Pd(NO₃)₂, RuO₂, ZrO₂, SiZrO₄, V₂O₅, NiO, Ni(NO₃)₂, NiCO₃, MnO, MnO₂,Mn₂O₃, Cr₂O₃ were tumbled in a suitable container for 15 to 30 minutesto mix the starting powders. The starting powder mixture was placed in aplatinum crucible and heated in air at a heating rate of 10° C./min to900° C. and then held at 900° C. for one hour to melt the mixture. Themelt was quenched from 900° C. by removing the platinum crucible fromthe furnace and pouring the melt onto a stainless steel platen. Theresulting material was ground in a mortar and pestle to less than 100mesh. The ground material was then ball-milled in a polyethylenecontainer with zirconia balls and isopropyl alcohol until the D₅₀ was0.5-0.7 microns. The ball-milled material was then separated from themilling balls, dried, and run through a 230 mesh screen to provide theflux powders used in the thick-film paste preparations.

TABLE 1 Glass frit compositions in weight percent Glass # PbO Li₂O TeO₂TeO₂/PbO 1 48.04 0.42 51.54 60:40 2 47.74 1.05 51.21 60:40 3 44.73 0.4354.84 63:37 4 55.49 0.41 44.09 53:47 5 58.07 0.41 41.52 50:50 6 34.512.44 63.06 72:28 7 42.77 0.43 56.80 65:35 8 45.82 4.99 49.19 60:40 948.04 0.42 51.53 60:40 10 47.82 0.89 51.29 60:40 11 42.77 0.43 56.8065:35 12 37.31 0.44 62.25 70:30 13 57.80 0.86 41.33 50:50 14 58.07 0.4141.52 50:50 Note: the compositions in the table are displayed as weightpercent, based on the weight of the total glass composition. TheTeO₂/PbO ratio is a molar ratio between only the TeO₂ and PbO of thecomposition.

TABLE 2 Glass frit compositions in weight percent TeO2/PbO Glass # (moleratio) Weight %--> SiO2 Al2O3 PbO ZrO2 B2O3 Nb2O5 Na2O Li2O Ta2O5 K2OAg2O CeO2 SnO2 TeO2 15 60:40 47.84 0.22 0.63 51.31 16 44:56 5.97 59.880.91 33.25 17 19:81 10.98 0.20 66.47 0.42 1.84 0.08 0.16 7.66 1.05 11.1318 69:31 36.19 1.92 3.21 58.68 18 69:31 36.19 1.92 3.21 58.68 19 70:3036.19 1.98 1.28 60.55 20 70:30 35.72 1.27 3.25 59.76 21 59.22 40.78Note: the compositions in the table are displayed as weight percent,based on the weight of the total glass composition. The TeO₂/PbO ratiois a molar ratio between only the TeO₂ and PbO of the composition.

TABLE 3 Combined frit composition resulting from the use of two fritsfrom Tables 1 and 2 as shown in the blended frit experiments of Tables10 and 11 Blended Glass Composition Weight % Number PbO Li2O Ag2O TeO2 A36.03 0.32 14.80 48.85 B 37.76 0.27 20.71 41.26 C 29.03 0.20 29.61 41.15Note: the compositions in the table are displayed as weight percent,based on the weight of the total glass composition.

TABLE 4 Glass frit compositions in weight percent TeO2/ PbO Weight Glass(mole % # ratio) ---> PbO TeO2 SiO2 Bi2O3 BiF3 Li2O SnO2 Al2O3 MgO 221.86 42.37 56.25 0.45 23 1.86 39.94 53.02 6.61 0.43 24 1.86 39.54 52.537.50 0.43 25 1.43 42.93 43.85 12.80 0.41 26 1.29 4208. 38.68 18.83 0.4027 1.43 42.54 43.46 6.35 7.24 0.41 28 1.49 47.01 50.18 0.55 1.84 29 1.6045.97 52.60 0.53 0.90 30 1.50 47.24 50.66 0.82 31 1.50 47.70 51.18 0.4332 1.50 47.36 50.81 0.43 33 1.50 46.67 50.06 0.43 34 1.57 45.34 50.930.50 35 1.50 46.32 49.70 0.44 36 1.50 46.19 49.55 0.43 37 1.50 46.8450.26 0.56 38 1.50 47.46 50.91 0.44 1.19 39 1.00 57.39 41.04 0.43 1.1540 1.50 46.75 50.14 0.44 41 1.22 53.14 46.44 0.42 42 0.50 66.70 23.858.98 0.47 43 0.75 62.09 33.29 4.18 0.44 44 1.50 46.98 50.40 0.44 45 1.5043.83 47.02 0.43 8.72 46 1.00 53.15 38.00 0.42 8.44 47 1.50 46.96 50.380.44 48 1.50 47.03 50.46 0.44 Glass # Na2O P2O5 SeO2 Co3O4 PdO RuO2 ZrO2V2O5 NiO MnO Cr2O3 22 0.93 23 24 25 26 27 28 0.43 29 30 1.29 31 0.70 321.40 33 2.84 34 3.23 35 3.54 36 3.83 37 2.34 38 39 40 2.67 41 42 43 442.18 45 46 47 2.22 48 2.08 Note: the compositions in the table aredisplayed as weight percent, based on the weight of the total glasscomposition. The TeO₂/PbO ratio is a molar ratio between only the TeO₂and PbO of the composition.

Example II Paste Preparation

Paste Preparation of the Examples in Tables 6, 7, 8, 9, 10, and 11

Paste preparations, in general, were prepared using the followingprocedure: The appropriate amount of solvents, binders, resins, andsurfactants from Table 5 were weighed and mixed in a mixing can for 15minutes to form the organic medium.

TABLE 5 Component Wt. % 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate5.57 Ethyl Cellulose (50-52% ethoxyl) 0.14 Ethyl Cellulose (48-50%ethoxyl) 0.04 N-tallow-1,3-diaminopropane dioleate 1.00 Hydrogenatedcastor oil 0.50 Pentaerythritol tetraester of perhydroabietic acid 1.25Dimethyl adipate 3.15 Dimethyl glutarate 0.35

Since Ag is the major part of the solids, it was added incrementally tothe medium to ensure better wetting. When well mixed, the paste wasrepeatedly passed through a 3-roll mill at progressively increasingpressures from 0 to 250 psi. The gap of the rolls was set to 2 mils. Thepaste viscosity was measured using a Brookfield viscometer andappropriate amounts of solvent and resin were added to adjust the pasteviscosity toward a target of between 230 and 280 Pa-sec. The degree ofdispersion was measured by fineness of grind (FOG). A typical FOG valuefor a paste is less than 20 microns for the fourth longest, continuousscratch and less than 10 microns for the point at which 50% of the pasteis scratched.

To make the final pastes used to generate the data in Tables 6, 7, 8, 9,10, and 11, 2 to 3 wt % of a frit from Table 1 was mixed into a portionof the Ag paste and dispersed by shear between rotating glass platesknown to one skilled in the art as a muller. Alternatively, two separatepastes were made by: 1) roll milling together appropriate amounts of Agwith the medium from Table 5; and 2) roll milling together appropriateamounts of frit from Table 1 with the medium from Table 5. Appropriateamounts of the Ag paste and the frit paste were then mixed togetherusing a planetary centrifugal mixer (Thinky Corporation, Tokyo, Japan)to form the tested pastes.

The paste examples of Tables 6, 7, 8, 9, 10, and 11 were made using theprocedure described above for making the paste compositions listed inthe table according to the following details. Tested pastes contained 85to 88% silver powder. The examples used a spherical silver with aD₅₀=2.0 μm.

To make the final pastes of Tables 10 & 11 three separate pastes weremade by 1) an appropriate amounts of Ag was added to an appropriateamount of the vehicle of Table 5 were rolled milled, 2) an appropriateamount of the 1st glass frit from Table 1 was added to appropriateamount of the vehicle of Table 5 were roll milled, and 3) an appropriateamount of the 2nd glass frit from Table 2 was added to the appropriateamount of vehicle of Table 5 was roll milled. Appropriate amounts of theAg paste and the frit pastes were mixed together using a planetarycentrifugal mixer (Thinky Corporation, Tokyo, Japan) as shown by thepaste compositions in Tables 10 & 11.

Table 3 shows the combined frit composition of the examples of Table 10& 11. The combined frit compositions shown in Table 3 are calculatedusing the frit compositions of Tables 1 and 2 in the blending ratio ofTables 10 & 11.

Thick-Film Paste Preparation of Examples in Tables 12, 13, 14, and 15

The organic components of the thick-film paste and the relative amountsare given in Table 5.

The organic components (˜4.6 g) were put into a Thinky mixing jar(Thinky USA, Inc.) and Thinky-mixed at 2000 RPM for 2 to 4 minutes untilwell blended. The inorganic components (Pb—Te—Li—O powders and silverconductive powders) were tumble-mixed in a glass jar for 15 min. Thetotal weight of the inorganic components was 44 g, of which 42.5-43.5 gwas silver powder and 0.5-1.5 g was the Pb—Te—Li—O powders of Table 1.One third of the inorganic components were then added to the Thinky jarcontaining the organic components and mixed for 1 minute at 2000 RPM.This was repeated until all of the inorganic components were added andmixed. The paste was cooled and the viscosity was adjusted to between200 and 500 Pa·s by adding solvent and then mixing for 1 minute at 2000RPM. This step was repeated until the desired viscosity was achieved.The paste was then roll-milled at a 1 mil gap for 3 passes at 0 psi and3 passes at 75 psi. The degree of dispersion was measured by fineness ofgrind (FOG). The FOG value is typically equal to or less than 20/10 forthick-film pastes. The viscosity of the paste was adjusted after 24hours at room temperature to between 200 and 320 Pa·s. Viscosity wasmeasured after 3 minutes at 10 RPM in a viscometer. The viscosity ofeach paste was measured on a Brookfield viscometer (Brookfield, Inc.,Middleboro, Mass.) with a #14 spindle and a #6 cup.

Example III Solar Cell Preparation

Solar Cell Preparation for the Examples Listed in Tables 6, 7, 8, 9, 10,and 11

Pastes were applied to 1.1″×1.1″ dicing-saw-cut multi-crystallinesilicon solar cells with a phosphorous-doped emitter on a p-type base.The pastes from Examples 1 and 13-22 were applied to DeutscheCell(DeutscheCell, Germany) multi-crystalline wafers with a 65Ω/□ emitterand pastes from Examples #2 through #6 were applied to Gintech (GintechEnergy Corporation, Taiwan) multi-crystalline wafers with a 55Ω/□0emitter. The solar cells used were textured by isotropic acid etchingand had an anti-reflection coating (ARC) of SiN_(x):H. Efficiency andfill factor, as shown in Table 6, 7, 8, 9, 10, and 11, were measured foreach sample. For each paste, the mean and median values of theefficiency and fill factor for 5 to 10 samples are shown. Each samplewas made by screen-printing using an ETP model L555 printer set with asqueegee speed of 250 mm/sec. The screen used had a pattern of 11 fingerlines with a 100 μm opening and 1 bus bar with a 1.5 mm opening on a 20μm emulsion in a screen with 325 mesh and 23 μm wires. A commerciallyavailable Al paste, DuPont PV381, was printed on the non-illuminated(back) side of the device.

The device with the printed patterns on both sides was then dried for 10minutes in a drying oven with a 250° C. peak temperature. The substrateswere then fired sun-side up with a CF7214 Despatch 6-zone IR furnaceusing a 560 cm/min belt speed and 550-600-650-700-800-905 to 945° C.temperature set points. The actual temperature of the part was measuredduring processing. The estimated peak temperature of each part was740-780° C. and each part was above 650° C. for a total time of 4seconds. The fully processed samples were then tested for PV performanceusing a calibrated ST-1000 tester.

Solar Cell Fabrication of the Examples of Tables 12, 13, 14, and 15

Solar cells for testing the performance of the thick-film paste weremade from 200 micron DeutscheCell (DeutscheCell, Germany)multi-crystalline silicon wafers with a 65 ohm/sq. phosphorous-dopedemitter layer which had an acid-etched textured surface and 70 nm thickPECVD SiN_(x) anti-reflective coating. The wafers were cut into 28 mm×28mm wafers using a diamond wafering saw. Wafers were screen-printed afterbeing cut down using an AMI-Presco MSP-485 screen printer to provide abus bar, eleven conductor lines at a 0.254 cm pitch, and a fullground-plane, screen-printed aluminum back-side conductor. Afterprinting and drying, cells were fired in a BTU International rapidthermal processing belt furnace. The firing temperatures shown in Tables12, 13, 14, and 15 were the furnace setpoint temperatures of the final,peak zone, which were approximately 125° C. greater than the actualwafer temperature. The fired conductor line median line width was 120microns and mean line height was 15 microns. The median line resistivitywas 3.0×10⁻⁶ ohm·cm. Performance of the 28 mm×28 mm cells is expected tobe impacted by edge effects that reduce the overall solar cell fillfactor (FF) by ˜5%.

Example IV Solar Cell Performance: Efficiency and Fill Factor

Test Procedure: Efficiency and Fill Factor for the Tables 6, 7, 8, 9,10, and 11

The solar cells built according to the method described herein weretested for conversion efficiency. An exemplary method of testingefficiency is provided below.

In an embodiment, the solar cells built according to the methoddescribed herein were placed in a commercial I-V tester for measuringefficiencies (Telecom STV, model ST-1000). The Xe Arc lamp in the I-Vtester simulated the sunlight with a known intensity, AM 1.5, andirradiated the front surface of the cells. The tester used a multi-pointcontact method to measure current (I) and voltage (V) at approximately400 load resistance settings to determine the cells' I-V curve. Bothfill factor (FF) and efficiency (Eff) were calculated from the I-Vcurve.

Solar Cell Electrical Measurements of the Examples of Tables 12, 13, 14and 15

Solar cell performance of the examples of Tables 12 and 13 was measuredusing a ST-1000, Telecom STV Co. IV tester at 25° C.±1.0° C. The Xe arclamp in the IV tester simulated sunlight with a known intensity, andirradiated the front surface of the cell. The tester used a four-contactmethod to measure current (I) and voltage (V) at approximately 400 loadresistance settings to determine the cell's I-V curve. Solar cellefficiency (Eff), fill factor (FF), and series resistance (Rs) (data notshown for Rs) were calculated from the I-V curve.

Median and mean values for efficiency and fill factor for these examplesare shown in Tables 12, 13, 14, and 15.

TABLE 6 Eff % results of pastes using selected glass frits EfficiencyEff % Example Glass Frit level 905 C. 915 C. 920 C. 925 C. 930 C. 940 C.945 C. # # (wt %) Mean Median Mean Median Mean Median Mean Median MeanMedian Mean Median Mean Median 1 1 2 14.32 14.63 15.45 15.60 2 1 2 14.0414.05 14.98 14.96 14.75 14.69 3 2 2 12.88 12.66 12.15 12.28 12.82 12.704 4 2 14.20 14.29 14.19 14.22 5 5 2 13.48 13.47 14.36 14.29 6 5 3 14.3414.69 14.33 14.24 14.08 14.28

TABLE 7 FF results of pastes using selected glass frits Fill Factor (FF)Example Glass Frit level 905 C. 915 C. 920 C. 925 C. 930 C. 940 C. 945C. # # (wt %) Mean Median Mean Median Mean Median Mean Median MeanMedian Mean Median Mean Median 1 1 2 71.24 72.72 75.91 76.18 2 1 2 71.3071.30 72.81 72.62 73.07 72.77 3 2 2 68.71 68.00 66.24 65.70 68.31 67.974 4 2 71.63 71.78 73.13 73.09 5 5 2 70.42 70.60 72.57 72.11 6 5 3 72.6573.60 72.59 72.17 71.91 72.73

TABLE 8 Eff % results of pastes using selected glass frits Efficiency(Eff %) Example Glass Frit level 880 C. 905 C. 920 C. 940 C. 945 C. # #(wt %) Mean Median Mean Median Mean Median Mean Median Mean Median 13 152 14.52 14.46 14 16 2 14.25 14.26 15 17 2 11.80 11.81 10.95 11.01 16 182 10.82 10.64 14.49 14.65 15.23 15.21 17 18 2 11.49 12.27 15.15 15.27 1819 2 14.25 14.26 14.92 14.93 19 20 2 12.66 12.71 14.74 14.84

TABLE 9 FF results of pastes using selected glass frits Fill Factor (FF)Example Glass Frit level 880 C. 905 C. 920 C. 940 C. 945 C. # # (wt %)Mean Median Mean Median Mean Median Mean Median Mean Median 13 15 270.98 70.90 14 16 2 71.33 71.15 15 17 2 59.43 59.30 56.59 57.14 16 18 256.01 54.80 72.96 73.67 75.75 76.00 17 18 2 58.34 60.67 76.32 76.88 1819 2 71.80 72.08 74.07 73.63 19 20 2 63.13 63.70 73.69 73.87

TABLE 10 Eff % results of pastes using selected glass frits 2nd BlendedGlass 1st Frit 2nd Frit Total Frit Efficiency (Eff %) Example 1st GlassComposition level level level 905 C. 915 C. 925 C. # Glass # # Number(wt %) (wt %) (wt %) Mean Median Mean Median Mean Median 20 5 21 B 1.971.03 3 14.52 14.50 14.96 14.99 14.79 14.67 21 5 21 C 1.5 1.5 3 14.9714.60 15.00 14.99 15.40 15.35 22 1 21 A 1.5 0.5 2 15.28 15.31 14.5114.47 15.01 15.20

TABLE 11 FF results of pastes using selected glass frits Blended 1st 2ndTotal 2nd Glass Frit Frit Frit Fill Factor (FF) Example 1st GlassComposition level level level 905 C. 915 C. 925 C. # Glass # # Number(wt %) (wt %) (wt %) Mean Median Mean Median Mean Median 20 5 21 B 1.971.03 3 73.96 74.93 75.49 75.53 75.53 75.63 21 5 21 C 1.5 1.5 3 73.6372.33 75.22 74.93 75.42 75.17 22 1 21 A 1.5 0.5 2 74.74 74.63 73.7473.65 75.28 75.77

TABLE 12 Eff % results of pastes using selected glass frits FritEfficiency Eff % Example Glass level 920 C. 930 C. 940 C. 950 C. 960 C.# # (wt %) Mean Median Mean Median Mean Median Mean Median Mean Median 79 2 15.12 14.97 15.45 15.36 15.34 15.40 15.37 15.37 15.36 15.41 8 10 214.83 14.74 14.98 14.92 14.83 14.76 15.20 15.30 15.19 15.15 9 11 2 15.1515.03 14.73 15.68 14.46 15.65 15.77 15.81 10 12 3 15.39 15.37 15.5215.58 15.55 15.56 15.49 15.34 15.66 15.83 11 13 2 15.13 15.25 15.1215.04 15.35 15.33 15.38 15.41 15.40 15.38 12 14 2 14.85 14.67 15.1215.19 15.17 15.07 15.57 15.36 15.50 15.59

TABLE 13 FF results of pastes using selected glass frits Frit FillFactor FF Example Glass level 920 C. 930 C. 940 C. 950 C. 960 C. # # (wt%) Mean Median Mean Median Mean Median Mean Median Mean Median 7 9 278.9 78.7 78.7 78.7 79.2 79.2 78.9 79.0 79.4 79.5 8 10 2 77.5 77.7 78.178.2 78.4 78.4 78.6 78.4 78.6 78.8 9 11 2 78.2 78.2 78.2 78.1 78.4 78.178.8 78.8 10 12 3 78.4 78.4 78.7 78.8 78.9 78.9 78.9 78.9 79.5 79.6 1113 2 78.0 77.9 78.6 78.7 79.1 79.0 79.0 78.9 79.1 79.2 12 14 2 77.5 78.479.0 78.8 78.7 78.8 78.7 79.1 78.8 78.9

TABLE 14 Eff % results of pastes using seleced glass frits Frit 910 C.920 C. 930 C. 940 C. 950 C. Example Glass level Eff. (%) Eff. (%) Eff.(%) Eff. (%) Eff. (%) Eff. (%) Eff. (%) Eff. (%) Eff. (%) Eff. (%) # #(wt %) mean median mean median mean median mean median mean median 24 383 14.82 14.97 15.20 15.23 15.05 15.08 14.37 14.37 25 39 1 14.56 14.5314.70 14.63 14.88 14.91 15.00 15.02 26 40 2 15.04 15.02 15.23 15.2914.85 14.77 14.99 15.07 15.11 15.09 27 41 2 14.82 14.74 14.96 15.1515.13 15.13 15.24 15.29 15.11 15.17 28 42 6 11.68 11.14 14.53 14.5314.54 14.63 15.11 14.99 14.97 14.99 29 43 4 12.85 13.22 14.39 14.5115.09 15.07 14.76 15.14 14.83 14.78 30 44 4 15.07 15.05 15.00 15.0615.32 15.31 15.17 15.13 15.17 15.13 31 22 2 13.48 13.66 15.27 15.3314.24 14.20 14.34 14.33 14.75 14.61 32 23 2 15.13 15.07 14.83 14.8215.40 15.37 15.59 15.64 15.42 15.42 33 24 2 15.09 15.14 15.37 15.3915.52 15.48 15.26 15.23 15.32 15.19 34 28 2 14.62 14.61 14.89 14.8514.78 14.80 14.35 14.24 13.97 14.06 35 29 3 15.00 15.05 15.27 15.2914.96 14.83 14.95 15.10 14.48 14.49 36 30 3 14.49 14.50 14.87 14.8315.43 15.39 15.30 15.24 15.33 15.34 37 31 2 14.91 14.81 13.99 14.4815.02 14.92 15.32 15.42 15.62 15.65 38 32 2.5 14.88 14.83 14.56 14.9415.01 15.28 15.12 15.17 14.56 14.86 39 33 3 14.64 14.67 14.96 14.8114.83 14.85 14.37 14.55 14.36 14.27 40 34 2.5 15.35 15.45 15.40 15.4015.62 15.61 15.69 15.57

TABLE 15 FF results of pastes using selected glass frits Frit 910 C. 920C. 930 C. 940 C. 950 C. Example Glass level FF FF FF FF FF FF FF FF FFFF # # (wt %) mean median mean median mean median mean median meanmedian 24 38 3 77.12 77.70 77.25 77.50 76.82 77.00 73.78 73.40 25 39 175.62 75.90 76.18 75.65 76.52 76.10 77.54 77.20 26 40 2 78.80 78.8078.94 78.90 78.90 79.05 79.03 78.90 78.72 79.10 27 41 2 77.84 77.5078.38 78.80 78.83 78.80 78.78 78.75 78.84 78.70 28 42 6 59.40 55.0073.68 71.80 73.84 74.80 77.08 77.20 77.08 76.80 29 43 4 51.22 53.7072.16 72.10 73.40 73.20 76.04 76.30 76.04 76.30 30 44 4 77.80 77.4078.80 78.90 78.80 79.00 78.50 79.10 78.50 79.10 31 22 2 70.03 70.1078.56 78.80 74.90 74.90 74.50 75.90 76.16 76.00 32 23 2 78.74 78.8078.74 78.90 78.90 79.00 79.36 79.20 79.20 79.20 33 24 2 78.88 78.8078.92 79.00 79.14 79.10 79.08 79.00 79.22 79.10 34 28 2 76.24 76.7076.96 77.40 75.94 76.40 73.40 73.90 71.70 72.80 35 29 3 77.06 77.6078.26 78.30 76.30 76.50 76.32 77.20 74.82 73.60 36 30 3 76.48 76.0077.72 77.60 78.94 79.10 79.06 79.20 78.90 78.90 37 31 2 76.38 76.2072.10 73.90 76.54 76.80 78.24 78.50 79.05 79.35 38 32 2.5 75.46 76.2074.10 76.40 76.80 77.00 76.78 77.10 75.04 76.00 39 33 3 74.86 75.0075.80 76.00 76.28 76.40 73.40 73.00 73.88 73.70 40 34 2.5 78.68 78.7078.68 78.60 79.44 79.40 79.16 79.10

Comparative Example I: Bismuth-Tellurium-Lithium-Oxide

Preparation of Bismuth-Tellurium-Lithium-Oxide

A bismuth-tellurium-lithium-oxide (Bi—Te—Li—O) containing composition asshown in Table 16 was prepared using boron oxide (B₂O₃), zinc oxide(ZnO), titanium oxide (TiO₂), bismuth oxide (Bi₂O₃), tellurium oxide(TeO₂), lithium carbonate (LiCO₃), and lithium phosphate (LiPO₄) and bythe procedure described above Example I: Lead-telliurium-lithium-oxidepreparation of glasses 1-7 of Table 1, and glasses of Tables 2 and 3.

TABLE 16 Bismuth-tellurium-lithium-oxide composition in weight percentof the oxides Glass A (wt %) B₂O₃ 2.09 ZnO 0.98 TiO₂ 0.48 Bi₂O₃ 26.64TeO₂ 67.22 P₂O₅ 0.43 Li₂O 2.16 Note: the composition in the table aredisplayed as weight percent, based on the weight of the total glasscompositionPaste Preparation

Pastes using glass A were made by the following procedure. A paste wasmade by mixing the appropriate amount of organic vehicle (Table 5) andAg powder. The Ag paste was passed through a 3-roll mill atprogressively increasing pressures from 0 to 75 psi. The Ag pasteviscosity was measured using a Brookfield viscometer and appropriateamounts of solvent and resin were added to adjust the paste viscositytoward a target of between 230 and 280 Pa-sec. Another paste was made bymixing the appropriate amount of organic vehicle (Table 5) and glasspowder A. The frit paste was passed through a 3-roll mill atprogressively increasing pressures from 0 to 250 psi. The degree ofdispersion of each paste was measured by fineness of grind (FOG). Atypical FOG value for a paste is less than 20 microns for the fourthlongest, continuous scratch and less than 10 microns for the point atwhich 50% of the paste is scratched.

Ag and frit pastes were mixed with a mixed together using a planetarycentrifugal mixer (Thinky Corporation, Tokyo, Japan) to make the finalpaste recipes displayed in Table 17.

Solar Cell Preparation and Efficiency and Fill Factor Measurement

Pastes were applied to 1.1″×1.1″ dicing-saw-cut multi-crystallinesilicon solar cells with a phosphorous-doped emitter on a p-type base.The pastes were applied to a DeutscheCell (DeutscheCell, Germany)multi-crystalline wafer with a 62 Ω/□ emitter. The solar cells used weretextured by isotropic acid etching and had an anti-reflection coating(ARC) of SiN_(x):H. Efficiency and fill factor, as shown in Table 17,were measured for each sample. Each sample was made by screen-printingusing a ETP model L555 printer set with a squeegee speed of 200 mm/sec.The screen used had a pattern of 11 finger lines with a 100 μm openingand 1 bus bar with a 1.5 mm opening on a 20 μm emulsion in a screen with325 mesh and 23 μm wires. A commercially available Al paste, DuPontPV381, was printed on the non-illuminated (back) side of the device.

The device with the printed patterns on both sides was then dried for 10minutes in a drying oven with a 250° C. peak temperature. The substrateswere then fired sun-side up with a CF7214 Despatch 6 zone IR furnaceusing a 560 cm/min belt speed and 500-550-610-700-800-HZ6 temperatureset points, where HZ6=885, 900 & 915° C. The actual temperature of thepart was measured during processing. The estimated peak temperature ofeach part was 745-775° C. and each part was above 650° C. for a totaltime of 4 seconds. The fully processed samples were then tested for PVperformance using a calibrated ST-1000 tester.

Efficiency and fill factor, shown in Table 17, were measured for eachsample. For each paste, the mean and median values of the efficiency andfill factor for 6 samples are shown.

TABLE 17 Comparative Example: Recipe and electrical performance forpastes containing the bismuth-tellurium-lithium-oxide glass A of Table16 Efficiency (Eff% ) Fill Factor (FF) Glass Ag Frit 900 915 930 900 915930 # wt % wt % Mean Median Mean Median Mean Median Mean Median MeanMedian Mean Median A 88.6 2.1 10.04 10.13 12.46 13.01 12.61 12.98 52.853.5 65.1 67.3 64.2 65.6 A 86.3 4.2 1.14 0.83 1.45 1.42 2.93 2.79 28.729.7 29.4 29.5 30.7 30.1

What is claimed is:
 1. A thick-film paste composition for use in formingan electrical connection in a photovoltaic device comprising asemiconductor substrate having at least one insulating layer on a mainsurface thereof, the composition comprising: (a) 97 to 99.75% by weightof an electrically conductive metal or derivative thereof, based ontotal solids in the composition; (b) 0.25 to 3% by weight based onsolids of a lead-tellurium-lithium-oxide that comprises: (i) at most 60%of PbO, (ii) more than 30% of TeO₂, and (iii) 0 to 5% of V₂O₅, all byweight of the lead-tellurium-lithium-oxide; and c) an organic medium,wherein the thick-film paste composition, when fired, is capable ofpenetrating the at least one insulating layer to form an electricalcontact with the photovoltaic device.
 2. The thick-film pastecomposition of claim 1, wherein the lead-tellurium-lithium-oxide ispresent as a homogeneous powder.
 3. The thick-film paste composition ofclaim 1, wherein the lead-tellurium-lithium-oxide is present as acombination of at least two powders having different compositions, suchthat the combination has an aggregate composition that comprises: (i) atmost 60% of PbO, (ii) more than 30% of TeO₂, and (iii) 0 to 5% of V₂O₅,all by weight of the aggregate of the lead-tellurium-lithium-oxide. 4.The thick-film paste composition of claim 3, wherein a first of the atleast two powders comprises some but not all of the elements of thegroup Pb, Te, Li, and O and a second of the at least two powderscomprises one or more of the elements of the group Pb, Te, Li, and O. 5.The thick-film paste composition of claim 1, wherein thelead-tellurium-lithium-oxide has a composition wherein the mole ratio oflead to tellurium is between 5/95 and 95/5.
 6. A thick-film pastecomposition for use in forming an electrical connection in aphotovoltaic device comprising a semiconductor substrate having at leastone insulating layer on a main surface thereof, the compositioncomprising: (a) 97 to 99.75% by weight of an electrically conductivemetal or derivative thereof, based on total solids in the composition;(b) 0.25 to 3% by weight based on solids of alead-tellurium-lithium-oxide that comprises 30-55 wt % PbO and 40-65 wt% TeO₂, all by weight of the lead-tellurium-lithium-oxide; and (c) anorganic medium, wherein the thick-film paste composition, when fired, iscapable of penetrating the at least one insulating layer to form anelectrical contact with the photovoltaic device.
 7. The thick-film pastecomposition of claim 1, wherein the lead-tellurium-lithium-oxide has acomposition that comprises 0 to 11% SiO₂, by weight of thelead-tellurium-lithium-oxide.
 8. A thick-film paste composition for usein forming an electrical connection in a photovoltaic device comprisinga semiconductor substrate having at least one insulating layer on a mainsurface thereof, the composition comprising: (a) 97 to 99.75% by weightof an electrically conductive metal or derivative thereof, based ontotal solids in the composition; (b) 0.25 to 3% by weight based onsolids of a lead-tellurium-lithium-oxide that comprises: (i) at most 60%of PbO and (ii) more than 30% of TeO₂, by weight of thelead-tellurium-lithium-oxide; and (c) an organic medium, wherein thethick-film paste composition, when fired, is capable of penetrating theat least one insulating layer to form an electrical contact with thephotovoltaic device.
 9. The thick-film paste composition of claim 1,wherein the lead-tellurium-lithium-oxide has a composition thatcomprises 0 to 10% B₂O₃, by weight of the lead-tellurium-lithium-oxide.10. The thick-film paste composition of claim 1, wherein thelead-tellurium-lithium-oxide comprises 0 to 10% B₂O₃, by weight of thelead-tellurium-lithium-oxide.
 11. The thick-film paste composition ofclaim 1, wherein the lead-tellurium-lithium-oxide is substantially freeof CdO.
 12. The thick-film paste composition of claim 1, wherein thelead-tellurium-lithium-oxide comprises 0.1-5 wt % Li₂O, by weight of thelead-tellurium-lithium-oxide.
 13. The thick-film paste composition ofclaim 1, wherein the electrically conductive metal comprises silver. 14.The thick-film paste composition of claim 1, wherein thelead-tellurium-lithium-oxide is at least partially crystalline.
 15. Thethick-film paste composition of claim 1, further comprising one or moreadditives selected from the group consisting of: GeO₂, Ga₂O₃, In₂O₃,NiO, CoO, ZnO, CaO, MgO, SrO, MnO, BaO, SeO₂, MoO₃, WO₃, Y₂O₃, As₂O₃,La₂O₃, Nd₂O₃, Bi₂O₃, Ta₂O₅, FeO, HfO₂, Cr₂O₃, CdO, Sb₂O₃, PbF₂, ZrO₂,Mn₂O₃, P₂O₅, CuO, La₂O₃, Pr₂O₃, Al₂O₃, Nd₂O₃, Gd₂O₃, Sm₂O₃, Dy₂O₃,Eu₂O₃, Ho₂O₃, Yb₂O₃, Lu₂O₃, CeO₂, BiF₃, SnO, B₂O₃, SiO₂, Ag₂O, Nb₂O₅,TiO₂, and metal halides selected from the group consisting of: NaCl,KBr, NaI, and LiF.
 16. The thick-film paste composition of claim 1,wherein the lead-tellurium-lithium-oxide further comprises oxides of oneor more elements selected from the group consisting of B, Si, Sn, Ti,Ag, Na, K, Rb, Cs, Ge, Ga, In, Ni, Zn, Ca, Mg, Sr, Ba, Se, Mo, W, Y, As,La, Nd, Co, Pr, Al, Gd, Sm, Dy, Eu, Ho, Yb, Lu, Bi, Ta, Fe, Hf, Cr, Cd,Sb, Bi, F, Zr, Mn, P, Cu, Ce, and Nb.
 17. A process comprising: (a)providing a semiconductor substrate comprising one or more insulatingfilms deposited onto at least one surface of the semiconductorsubstrate; (b) applying a thick-film paste composition onto at least aportion of the insulating film to form a layered structure, wherein thethick-film paste composition comprises: (i) 97 to 99.75% by weight of anelectrically conductive metal or derivative thereof, based on totalsolids in the composition; (ii) 0.25 to 3% by weight based on solids ofa lead-tellurium-lithium-oxide that comprises at most 60% of PbO, morethan 30% of TeO₂, and 0 to 5% of V₂O₅, all by weight of thelead-tellurium-lithium-oxide; and (iii) an organic medium; and (c)firing the semiconductor substrate, one or more insulating films, andthick-film paste wherein the organic medium of the thick-film paste isvolatilized, forming an electrode in contact with the one or moreinsulating films and in electrical contact with the semiconductorsubstrate.
 18. The process of claim 17, wherein thelead-tellurium-lithium-oxide is present as a combination of at least twopowders having different compositions, such that the combination has anaggregate composition that comprises at most 60% of PbO, more than 30%of TeO₂, and 0 to 5% V₂O₅, by weight of the aggregate of thelead-tellurium-lithium-oxide.
 19. The process of claim 18, wherein afirst of the at least two powders comprises some but not all of theelements of the group Pb, Te, Li, and O and a second of the at least twopowders comprises one or more of the elements of the group Pb, Te, Li,and O.
 20. An article comprising: (a) a semiconductor substrate; (b) oneor more insulating layers on the semiconductor substrate; and (c) anelectrode in contact with the one or more insulating layers and inelectrical contact with the semiconductor substrate, the electrodecomprising an electrically conductive metal and alead-tellurium-lithium-oxide, and wherein, prior to firing, thelead-tellurium-oxide has a composition that comprises at most 60% ofPbO, more than 30% of TeO₂, and 0 to 5% V₂O₅.
 21. The article of claim20, wherein the article is a semiconductor device.
 22. The article ofclaim 21, wherein the semiconductor device is a solar cell.
 23. Anarticle, having been formed by the process of claim
 17. 24. A thick-filmpaste composition comprising: (a) 85 to 99.75% by weight of anelectrically conductive metal or derivative thereof, based on totalsolids in the composition; (b) 0.25 to 15% by weight based on solids ofa lead-tellurium-lithium-oxide composition, with the provisos that thelead-tellurium-lithium-oxide has a composition that comprises (i) atmost 60% of PbO, (ii) more than 30% of TeO₂, and (iii) 0 to 5% V₂O₅, byweight of the lead-tellurium-lithium-oxide, and thelead-tellurium-lithium-oxide is a combination of at least two powdershaving different compositions; and (c) an organic medium.
 25. Thethick-film paste composition of claim 24, wherein a first of the atleast two powders comprises some but not all of the elements of thegroup Pb, Te, Li, and O and a second of the at least two powderscomprises one or more of the elements of the group Pb, Te, Li, and O.